EP1090883A2 - Process for increasing the concentration of diluted brine in NaCl electrolysis plants that work along the membrane process - Google Patents

Process for increasing the concentration of diluted brine in NaCl electrolysis plants that work along the membrane process Download PDF

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Publication number
EP1090883A2
EP1090883A2 EP00120220A EP00120220A EP1090883A2 EP 1090883 A2 EP1090883 A2 EP 1090883A2 EP 00120220 A EP00120220 A EP 00120220A EP 00120220 A EP00120220 A EP 00120220A EP 1090883 A2 EP1090883 A2 EP 1090883A2
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Prior art keywords
salt
brine
nacl
silo
concentration
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EP00120220A
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German (de)
French (fr)
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EP1090883B1 (en
EP1090883A3 (en
Inventor
Alfred Soppe
Klaus Dr. Geisler
Bernd Dr. Bressel
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Covestro Deutschland AG
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Bayer AG
Bayer MaterialScience AG
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the cells In order to maintain the electrolysis process, the cells must constantly have so much Strong brines are tracked that the salt concentration in the running thin brine (Anolyte) does not meet the minimum concentration required by the membrane manufacturer falls below. This is around 170 g NaCl per liter. Usually the exhaustion the brine is limited to 200 to 220 g NaCl per liter.
  • the amount of salt supplied to the electrolytic cell with the brine is thus approx. 40% exploited.
  • the thin brine that runs off becomes economic and ecological Recycled, i.e. after dechlorination with strong salt and after appropriate cleaning of the electrolytic cell supplied again.
  • the missing amount of water is added to make up the to compensate for the amount of liquid escaping through the membrane.
  • the brine In conventional brine fortification plants, the brine is usually from below passed upwards through containers (quick dissolver) with crystalline salt. It strengthens the brine. The salt is continuously fed through mechanical conveyors given in the quick release.
  • the Thin brine placed in open salt stores and strengthened there (Ullmann Encyclopedia technical chemistry; Chapter chlorine and sodium chloride; Scouce, chlorine, Reinhold Publishing Corp .; UNITED STATES; 1962).
  • the salt is either with automatic conveyor systems or by means of Wheel loader removed from a corresponding dry salt warehouse.
  • the salt used here has to be used for reasons of Storage stability can be doped with anti-caking agents (e.g. potassium hexacyanoferrate), which leads to a deterioration in the current yield in the electrolysis process (cf. W. Versteegen, report from Akzo Nobel, title: Decomposition of Ironhexacyanides in alkaline Brine of Chlorin-Caustic Plants during disolution and Brine treatment, Author: J.H.G. van der Steegen, March 26, 1990).
  • anti-caking agents e.g. potassium hexacyanoferrate
  • NaCl salt without the addition of anti-caking agents stored in a silo and can be dosed easily from there, when the NaCl salt is mixed with water, such that there is always a supernatant liquid is guaranteed.
  • the protrusion varies according to the size of the silo and its geometric size Design. It should be chosen so that the salt does not fall dry. If necessary, make up water during the dosing process.
  • the present invention accordingly relates to a method for strengthening Thin brine in NaCl electrolysis plants using the membrane process, which thereby is characterized in that the salt in a mass flow silo with liquid supernatant saved and from there continuously the quick release or preferably is fed directly to the thin brine current.
  • the salt is ensiled so that the salt bed with saturated brine or water is covered. Since the removal of the Water / NaCl salt mixture to reduce the supernatant liquid needs to be refilled of water ensure that there is a minimum overhang of 20 cm preserved.
  • the excess brine is used to suppress bridging and that Rinse out crystalline salt from the outlet port of the silo. This is enough relatively small amounts of liquid to discharge the salt.
  • the silo should be dimensioned so that the filter resistance generated by the salt creates a fluid flow capable of delivering the desired amount of salt dosing out.
  • Mass flow silos are preferred as silos. In general silos of this type have the following dimensions: diameter 5 to 12 m, height 10 up to 25 m.
  • the amount of liquid seeping through the silo content can be assumed if one resting solid in the silo z. B. with the help of known calculation documents e.g. prove for the groundwater flow and estimate the magnitude.
  • a brine containing approx. 250 g / l is led past from the outlet nozzle and by a pump via a quantity and a radiometric density measurement for next process step (brine filtration).
  • a control valve is controlled, which doses enough salt slurry into the brine flow to produce an almost saturated brine with a density of 1.198 g / m 3 .
  • the specified density value is set again within 60 seconds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Strengthening sols in a sodium chloride (NaCl) electrolysis apparatus comprises storing the required NaCl salt in a mass flow silo with a liquid supernatant and continuously adding to the solutizer.

Description

Bei der Erzeugung von Chlor und Natronlauge nach dem Membranverfahren wird nahezu gesättigte NaCl-Lösung (Sole) in den Elektrolyseur geführt. Dort werden mittels Gleichstrom in die gewünschten Produkte Chlor, Natronlauge und Wasserstoff erzeugt. Dabei reduziert sich die Salzkonzentration in der Sole um 80 bis 130 g/l. Beim Elektrolysevorgang reduziert sich außerdem die in der Elektrolysezelle befindliche Solemenge um 3 bis 4 Mol H2O je Mol erzeugter NaOH.When chlorine and caustic soda are produced using the membrane process, almost saturated NaCl solution (brine) is fed into the electrolyzer. There, chlorine, sodium hydroxide solution and hydrogen are generated in the desired products using direct current. The salt concentration in the brine is reduced by 80 to 130 g / l. During the electrolysis process, the amount of brine in the electrolysis cell is also reduced by 3 to 4 moles of H 2 O per mole of NaOH produced.

Um den Elektrolysevorgang aufrecht zu erhalten, muss den Zellen ständig soviel Starksole nachgeführt werden, dass die Salzkonzentration in der ablaufenden Dünnsole (Anolyt) die vom Membranhersteller geforderte Mindestkonzentration nicht unterschreitet. Diese liegt bei ca. 170 g NaCl pro Liter. Üblicherweise wird die Auszehrung der Sole bis auf 200 bis 220 g NaCl pro Liter beschränkt.In order to maintain the electrolysis process, the cells must constantly have so much Strong brines are tracked that the salt concentration in the running thin brine (Anolyte) does not meet the minimum concentration required by the membrane manufacturer falls below. This is around 170 g NaCl per liter. Usually the exhaustion the brine is limited to 200 to 220 g NaCl per liter.

Die der Elektrolysezelle mit der Sole zugeführte Salzmenge wird somit zu ca. 40 % ausgenutzt. Die ablaufende Dünnsole wird aus ökonomischen und ökologischen Gründen recycelt, d.h. nach der Entchlorung mit festem Salz wieder aufgestärkt und nach entsprechender Reinigung der Elektrolysezelle erneut zugeführt. Vor der Aufstärkung mit kristallinem Salz wird die fehlende Wassermenge zugegeben, um die durch die Membran entweichende Flüssigkeitsmenge auszugleichen.The amount of salt supplied to the electrolytic cell with the brine is thus approx. 40% exploited. The thin brine that runs off becomes economic and ecological Recycled, i.e. after dechlorination with strong salt and after appropriate cleaning of the electrolytic cell supplied again. Before fortification with crystalline salt, the missing amount of water is added to make up the to compensate for the amount of liquid escaping through the membrane.

In herkömmlichen Sole-Aufstärkungsanlagen wird die Sole üblicherweise von unten nach oben durch Behälter (Schnellöser) mit kristallinem Salz geleitet. Dabei stärkt sich die Sole auf. Das Salz wird hierbei kontinuierlich über mechanische Fördereinrichtungen in den Schnellöser gegeben. Bei einem alternativen Verfahren wird die Dünnsole in offene Salzlager gegeben und dort aufgestärkt (Ullmann Encyclopädie der technischen Chemie; Kapitel Chlor und Natriumchlorid; Scouce, Chlorine, Reinhold Publishing Corp.; USA; 1962). In conventional brine fortification plants, the brine is usually from below passed upwards through containers (quick dissolver) with crystalline salt. It strengthens the brine. The salt is continuously fed through mechanical conveyors given in the quick release. In an alternative method, the Thin brine placed in open salt stores and strengthened there (Ullmann Encyclopedia technical chemistry; Chapter chlorine and sodium chloride; Scouce, chlorine, Reinhold Publishing Corp .; UNITED STATES; 1962).

Dabei wird das Salz entweder mit automatischen Förderanlagen oder mittels Radschaufelladern einem entsprechenden Trockensalzlager entnommen.The salt is either with automatic conveyor systems or by means of Wheel loader removed from a corresponding dry salt warehouse.

Die aus dem Stand der Technik bekannten Verfahren sind mit einer Reihe von Nachteilen behaftet.The methods known from the prior art are compatible with a number of Disadvantages.

Wenn möglich wird der Schnellöser direkt, ohne Zwischenlagerung, aus dem Salztransportweg beschickt. Das hierbei verwendete Salz muss aber aus Gründen der Lagerfähigkeit mit Antibackmitteln (z. B. Kaliumhexacyanoferrat) dotiert werden, was zu einer Verschlechterung der Stromausbeute im Elektrolyseprozess führt (vgl. W. Versteegen, Bericht v. Akzo Nobel, Titel: Decomposition of Ironhexacyanides in alkaline Brine of Chlorin-Caustic Plants during disolution and Brine treatment, Autor: J.H.G. van der Steegen, 26.03.1990).If possible, the quick release becomes directly from the salt transport route without intermediate storage loaded. The salt used here has to be used for reasons of Storage stability can be doped with anti-caking agents (e.g. potassium hexacyanoferrate), which leads to a deterioration in the current yield in the electrolysis process (cf. W. Versteegen, report from Akzo Nobel, title: Decomposition of Ironhexacyanides in alkaline Brine of Chlorin-Caustic Plants during disolution and Brine treatment, Author: J.H.G. van der Steegen, March 26, 1990).

Offene Lösegruben führen zu salzhaltiger Schwadenbildung, die ihrerseits an den umliegenden Einrichtungen erhebliche Korrosionsschäden hervorruft. Außerdem geht hierbei durch das Entweichen von Dampf unnötig viel Wärme verloren, die danach durch Beheizung wieder zugeführt werden muss.Open release pits lead to the formation of salty swaths, which in turn attach to the surrounding facilities causes significant corrosion damage. Moreover the steam escapes unnecessarily much heat, which must then be supplied again by heating.

Außerdem sind mechanische Fördereinrichtungen zur Beschickung von Schnellösern sind dem ständigen Verschleiß unterlegen, benötigen hohen Wartungsaufwand und entsprechende personalintensive Beaufsichtigung und Bedienung.There are also mechanical conveyors for loading quick release are subject to constant wear, require high maintenance and appropriate personnel-intensive supervision and operation.

Ziel der vorliegenden Erfindung war es, ein Verfahren zur Aufstärkung von Dünnsole zur Verfügung zu stellen, dass die vorgenannten Nachteile vermeidet und:

  • automatisch aus einem Lagervorrat (Silo) die Dünnsole aufstärkt
  • nicht auf Antibackmittelzusätze zur Erzeugung der Lagerfähigkeit angewiesen ist,
  • geringe Wärmeverluste aufweist
  • große Mengen an Salz bereithält
  • nicht auf mechanische Transporteinrichtungen angewiesen ist.
The aim of the present invention was to provide a method for strengthening thin brine which avoids the aforementioned disadvantages and:
  • the thin brine is automatically strengthened from a stock (silo)
  • does not depend on anti-caking agent additives to generate shelf life,
  • has low heat losses
  • holds large amounts of salt ready
  • does not rely on mechanical transport devices.

Trockenes oder nahezu trockenes NaCl-Salz mit einer Restfeuchte von 1 - 3 % ist jedoch nicht silierfähig, es neigt zu Brückenbildung und Verbackung und macht eine zuverlässige Ausdosierung unmöglich.Dry or almost dry NaCl salt with a residual moisture of 1 - 3% however not capable of ensiling, it tends to form bridges and cake and makes one reliable dosing impossible.

Überraschenderweise wurde gefunden, dass NaCl-Salz ohne Zusatz von Antibackmitteln in einem Silo gespeichert und von dort problemlos dosiert werden kann, wenn das NaCl-Salz mit Wasser versetzt wird, derart, dass stets ein Flüssigkeitsüberstand gewährleistet ist. Der Überstand variiert nach Silogröße und dessen geometrischer Ausgestaltung. Er ist so zu wählen, daß das Salz nicht trockenfällt. Gegebenenfalls ist Wasser während des Ausdosiervorgangs nachzuspeisen.Surprisingly, it was found that NaCl salt without the addition of anti-caking agents stored in a silo and can be dosed easily from there, when the NaCl salt is mixed with water, such that there is always a supernatant liquid is guaranteed. The protrusion varies according to the size of the silo and its geometric size Design. It should be chosen so that the salt does not fall dry. If necessary, make up water during the dosing process.

Die vorliegende Erfindung betrifft demnach ein Verfahren zur Aufstärkung von Dünnsole in NaCl-Elektrolyseanlagen nach dem Membranverfahren, welches dadurch gekennzeichnet ist, dass das Salz in einem Massenfluß-Silo mit Flüssigkeitüberstand gespeichert und von dort kontinuierlich dem Schnellöser oder vorzugsweise direkt dem Dünnsolestrom zugeführt wird.The present invention accordingly relates to a method for strengthening Thin brine in NaCl electrolysis plants using the membrane process, which thereby is characterized in that the salt in a mass flow silo with liquid supernatant saved and from there continuously the quick release or preferably is fed directly to the thin brine current.

Bei der vorliegenden Erfindung wird das Salz so siliert, dass die Salzschüttung mit gesättigter Sole oder Wasser überdeckt ist. Da sich bei der Entnahme der Wasser/NaCl-Salz-Mischung der Flüssigkeitsüberstand verringert, muss durch Nachfüllen von Wasser sichergestellt werden, dass ein Mindesüberstand von 20 cm erhalten bleibt.In the present invention, the salt is ensiled so that the salt bed with saturated brine or water is covered. Since the removal of the Water / NaCl salt mixture to reduce the supernatant liquid needs to be refilled of water ensure that there is a minimum overhang of 20 cm preserved.

Die überstehende Sole wird dazu benutzt, Brückenbildung zu unterdrücken und das kristalline Salz aus dem Auslaufstutzen des Silos auszuspülen. Hierbei genügen relativ kleine Flüssigkeitsmengen um das Salz auszutragen.The excess brine is used to suppress bridging and that Rinse out crystalline salt from the outlet port of the silo. This is enough relatively small amounts of liquid to discharge the salt.

Das Silo ist so zu dimensionieren, dass der durch das Salz erzeugte Filterwiderstand einen Flüssigkeitsdurchfluß erzeugt, der in der Lage ist, die gewünschte Salzmenge auszudosieren. Als Silos eignen sich bevorzugt Massenfluß-Silos. Im allgemeinen besitzen Silos dieser Art folgende Dimensionen: Durchmesser 5 bis 12 m, Höhe 10 bis 25 m.The silo should be dimensioned so that the filter resistance generated by the salt creates a fluid flow capable of delivering the desired amount of salt dosing out. Mass flow silos are preferred as silos. In general silos of this type have the following dimensions: diameter 5 to 12 m, height 10 up to 25 m.

Die durch den Siloinhalt sickernde Flüssigkeitsmenge lässt sich bei Annahme eines ruhenden Feststoffes im Silo z. B. mit Hilfe bekannter Berechnungsunterlagen z.B. für die Grundwasserströmung nachweisen und größenordnungsmäßig abschätzen.The amount of liquid seeping through the silo content can be assumed if one resting solid in the silo z. B. with the help of known calculation documents e.g. prove for the groundwater flow and estimate the magnitude.

Die mathematische Berechnung zeigt, dass in einem üblichen Massenfluß-Silo auch bei feinteiligem Salz genügend Sickerflüssigkeit zum Austrag der in einer Membranelektrolyse erforderlichen Salzmenge zur Verfügung steht.The mathematical calculation shows that in a usual mass flow silo too In the case of fine-particle salt, sufficient seepage liquid to discharge the membrane electrolysis required amount of salt is available.

Andererseits zeigen Versuche, dass der Flüssigkeitsanteil im Austrag kleiner ist, als die im Solekreislauf benötigte Zusatzwassermenge. Dies erweist sich als vorteilhaft für das NaCl-Membranverfahren, da der Wasserzusatz auf diese Weise je nach Bedarf gesteuert werden kann. On the other hand, tests show that the proportion of liquid in the discharge is less than the amount of make-up water required in the brine circuit. This proves to be advantageous for the NaCl membrane process, as the water addition in this way depends on Demand can be controlled.

Beispielexample

In einem 20 m3-Behälter mit konischem Boden und Auslaufstutzen werden 20 t Siedesalz ohne Antibackmittel gefüllt und so lange mit vollentsalztem Wasser überschichtet, bis die überstehende Wasserschicht ca. 20 cm beträgt.In a 20 m 3 container with a conical bottom and discharge nozzle, 20 t of evaporated salt are filled without anti-caking agents and covered with deionized water until the overlying water layer is approx. 20 cm.

Aus Auslaufstutzen wird eine ca. 250 g/l enthaltende Salzsole vorbeigeführt und von einer Pumpe über eine Mengen- und eine radiometrische Dichtemessung zum nächsten Prozeßschritt (Solefiltration) gedrückt.A brine containing approx. 250 g / l is led past from the outlet nozzle and by a pump via a quantity and a radiometric density measurement for next process step (brine filtration).

Mit Hilfe der radiometrischen Dichtemessung wird ein Regelventil angesteuert, das soviel Salzslurry in den Solestrom eindosiert, dass eine nahezu gesättigte Sole mit einer Dichte von 1,198 g/m3 entsteht.With the help of the radiometric density measurement, a control valve is controlled, which doses enough salt slurry into the brine flow to produce an almost saturated brine with a density of 1.198 g / m 3 .

Nach Halbierung der verdünnten Solemenge, die aufgestärkt werden soll, ist nach ca. 90 sec wieder auf den o. a. Wert von 1,198 g/m3 eingeregelt.After halving the amount of dilute brine to be strengthened, the above-mentioned value of 1.198 g / m 3 is adjusted again after about 90 seconds.

Wird die Pumpenleistung wieder erhöht, stellt sich der vorgegebene Dichtewert innerhalb von 60 Sekunden erneut ein.If the pump output is increased again, the specified density value is set again within 60 seconds.

Bei einem mittleren Solestrom ca. 2,1 m3/h ist das Salz nach 83 h vollständig aus dem Silo ausdosiert, während die überstehende Flüssigkeit noch ein Drittel der Höhe des Auslaufkonus verdeckt.With an average brine flow of approx. 2.1 m 3 / h, the salt is completely dosed out of the silo after 83 h, while the excess liquid still covers a third of the height of the outlet cone.

Claims (4)

Verfahren zur Aufstärkung von Dünnsole in NaCl-Elektrolyseanlagen nach dem Membranverfahren dadurch gekennzeichnet, dass das erforderliche NaCl-Salz in einem Massenfluß-Silo mit Flüssigkeitsüberstand gespeichert und von dort kontinuierlich dem Schnellöser zugeführt wird.Process for strengthening thin brine in NaCl electrolysis plants the membrane process characterized in that the required NaCl salt stored in a mass flow silo with a supernatant and is continuously fed from there to the quick release. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das Salz/Wasser-Gemisch direkt dem Dünnsolestrom zugeführt wird.A method according to claim 1, characterized in that the salt / water mixture is fed directly to the thin brine current. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Salz mit mechanischen Fördereinrichtungen dem Silo zugeführt wird.A method according to claim 1, characterized in that the salt with mechanical conveyors are fed to the silo. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Salz über hydraulische Förderung in das Silo eingebracht wird.A method according to claim 1, characterized in that the salt over hydraulic conveying is introduced into the silo.
EP00120220A 1999-10-08 2000-09-26 Process for increasing the concentration of diluted brine in NaCl electrolysis plants that work along the membrane process Expired - Lifetime EP1090883B1 (en)

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DE19948588A DE19948588A1 (en) 1999-10-08 1999-10-08 Process for strengthening thin brine in NaCI electrolysis plants using the membrane process
DE19948588 1999-10-08

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US20060280907A1 (en) * 2005-06-08 2006-12-14 Whitaker Robert H Novel mineral composition
US20070104923A1 (en) * 2005-11-04 2007-05-10 Whitaker Robert H Novel mineral composition
US7833339B2 (en) 2006-04-18 2010-11-16 Franklin Industrial Minerals Mineral filler composition
US7651559B2 (en) 2005-11-04 2010-01-26 Franklin Industrial Minerals Mineral composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4459188A (en) * 1982-09-13 1984-07-10 Texas Brine Corporation Brine systems for chlor-alkali membrane cells
US4528168A (en) * 1983-10-14 1985-07-09 The Dow Chemical Company Brine saturator method of operation

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Publication number Priority date Publication date Assignee Title
US541146A (en) * 1895-06-18 blaokman
JPS6135897A (en) * 1984-07-30 1986-02-20 Nippon Atom Ind Group Co Ltd Waste sludge discharge apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4459188A (en) * 1982-09-13 1984-07-10 Texas Brine Corporation Brine systems for chlor-alkali membrane cells
US4528168A (en) * 1983-10-14 1985-07-09 The Dow Chemical Company Brine saturator method of operation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
, ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY FIFTH, COMPLETELY REVISED EDITION, 1986 , VOLUME A 6: CERAMICS TO CHLOROHYDRINS, PAGES 406 - 410 XP002252536 * Seite 409 * *

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ATE409169T1 (en) 2008-10-15
PL194756B1 (en) 2007-07-31
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PL342987A1 (en) 2001-04-09
EP1090883B1 (en) 2008-09-24
JP4977290B2 (en) 2012-07-18
CZ301196B6 (en) 2009-12-02
EP1090883A3 (en) 2003-10-29
US6547948B1 (en) 2003-04-15
DE50015370D1 (en) 2008-11-06

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